Aza compounds of high molecular weight



Patented June 27, 1939 PATENT OFFICE AZA COMPOUNDS OF HIGH MOLECULAR WEIGHT Karl Koeliei'ie, tudwis'haten nane-Rh ne, Ger many, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application mm, 1937,,Serial No.

I 141,245. In Germany May 22, 1936 5 Claims.

The present invention relates to new aza compounds.

I have found that new and valuable aza compounds are obtained by acting on benzanthrones having a group:-

in peri-position to a (JO-group (in which R1 may be hydrogen or an alkyl group and R2 may be; hydrogen or an alkyl, aryl or acylgroup') with; compounds which permit of the conversion into;

a ring of the part of the molecule:-

Different methods may be adopted for the conversion of the said part of the molecule into a ring, epending on the significance of RI When R1 and R2 are hydrogen; compounds'which are capable of forming a ring with the two groups in peri-position while retaining the nitrogen atom of the amino group in peri-position are allowed to act on the initial materials. For this purpose there may be mentioned for example amides, nitriles and esters: of carboxylic acids, such as urea, cyanamide, formamide, acetamide, lauric acid amide, amides of benzene carboxylic acids, hexahydrobenzamide, quinoline carboxylic acid amides and the corresponding nitriles, esters of acyl-acetic acids, malonic acids, cyanoacetic acid, urethanes, and also ketones, such as acetone";-

methyl ethyl ketone, methyl phenyl ketone, methyl lauryl ketone andcyclohexanone. The reaction is usually carried out while heating and in the presence of a condensing agent. For example the reaction with amidesor nitriles is preferably carried out in the presence of acid substances, such as boric acid, ammonium chloride, ammonium bisulphate or mineral acids. In many cases copper or copper compounds may also be employed. For the reactionof aminobenzanthrones of the said kind with acid esters or ketones, on the other hand, it is preferable to use alkaline agents, such as alkali metal hydroxides,

alkali metal carbonates, alkali metal acetates or alkaline earth metal hydroxides.

The initial materials may also be compounds in which R1 is hydrogen or an alkyl group and R2 is an alkyl or aryl group. In order to effect ring closure, these substances are treated with acid agents, sulphuric acid or anhydrous aluminium halides for example being suitable for the purpose. When starting from compounds in which R1 is hydrogen or an alkyl group and R2 is an acyl group, it is preferable to use alkaline agents. In the two last-mentioned cases, i. e. when the amino group already contains the organic radicle necessary for the information of the ring, it is thus sufficient to treat the initial materials with an acid or basic agentQwhile for'the conversion of the free amino compounds into the new aza compounds it is necessary to use an organic substance of the kinddescribed at the beginning of this paragraph, but the simultaneous use of an acidi'or alkaline agent is only preferable.

'A further method for the preparation of the said compounds consists in treating aza compounds having the following composition whichncontain in one of the positions marked y a nitrogen atom which is a member of a B-membere'd ringuatta'ched to the position marked :r, with compounds capable of building up an isocycli-csfi-membered ring from the keto group to on'e tofi fthe remainingpe'ri positions, i. e. 'a position para to onemarked y.

In many cases the preparation of the initial materials and the addition of the ring according to this invention may be carried out in one working operation. In many cases there may nausea; instead of the aminobenzanthrones, the corresponding nitrobenzanthrones, for example when the reaction is carried out with the aid of formarjnide' or urea. Instead of the acylaminobenz'anthrones, the corresponding amidines may also be used. g

a new aza compounds are usually obtained ir'i gave yields and in the pure state. When necessary they may be purified and separated from any compounds formed at the same time in the usual manner, as for example by dissolution and precipitation, sublimation, by way of their salts with strong acids or by treatment with oxidizing agents. Some of the products are basic dyestufis, others are suitable for dyeing acetate artificial silk, coloring lacquers, waxes, oils, hydrocarbons and the like, and some may be employed for the preparation of dyestufis or medicaments.

The following examples will further illustrate how the said invention may be carried out in practice, but the invention is not restricted to these examples. The parts are by weight.

Example 1 A mixture of 25 parts of 5-aminobenzanthrone, 25 parts of ammonium bisulphate, 50 parts of nitrobenzene and parts of formamide is heated to boiling while stirring until a sample withdrawn no longer contains unchanged 5-aminobenzanthrone. The whole is allowed to cool and the yellow powder, obtained in an excellent yield, filtered off by suction. It dissolves in concentrated sulphuric acid giving a red coloration and ablue overflow coloration. The compound is also soluble in dilute acids and dyes vegetable fibres yellow shades therefrom. It dyes acetate artificial silk yellow shades from an acetic acid or alkaline bath. According to analysis and its properties it is 10.12- diazaperylene:-

which melts at from 254 to 255 C.

Instead of 5-aminobenzanthrone, its alkyl, amino, halogen, nitro, cyano, sulphonic acid or carboxylic acid derivatives may be used as initial materials. Other acid amides, as for example acetamide or benzamide, may be used instead of formamide. The corresponding ll-alkylor 11- aryl-lO.l2-diazaperylenes are thus obtained. Such compounds are also obtained by heating 5- aminobenzanthrone with arylmethylimide chlorides or by heating 5-aroylaminobenzanthrones with ammonia under pressure. Furthermore 5- aminobenzanthrone may be caused to react for example with benzotrinitrile in the presence of hydrochloric acid. From 5-amino-8-azabenzanthrone and formamide, 7.10.12-triazaperylene is obtained.

Instead of ammonium bisulphate, hydrochloric acid, boric acid, sulphuric acid, sulphur dioxide or ammonium chloride may be used for example, but their use is not essential.

Example 2 A mixture of 25 parts of 5-aminobenzanthrone, 600 parts of 2 per cent caustic soda solution and 400 parts of acetone is heated at C. in a pressure-tight vessel until a sample withdrawn no longer contains unchanged 5-amino-benzanthrone. The whole is allowed to cool and, is worked up in the usual manner. The ll-methyllo-azaperylene thus obtained dissolves in concentrated sulphuric acid giving a golden yellow coloration and a green fluorescence. It forms yellow needles and melts at from 218 to 219 C. Its solutions in benzene and alcohol have a powerful blue-green fluorescence.

In a corresponding manner 6.7-benzo-9-methyl-lO-azapyrene is obtained from 4-aminobenzanthrone and acetone.

Example 3 A mixture of 20 parts of 4-aminobenzanthrone, 40' parts of nitrobenzene, 20 parts of formamide and 20 parts of ammonium bisulphate is heated to boiling while stirring until a sample withdrawn no longer contains unchanged initial material. The whole is allowed to cool and the mixture is worked up in the manner described in Example 1. The 6.7-benzo-8.10-diazapyrene:-

Example 4 A mixture of 25 parts of 5-aminobenzanthrone, 100 parts of nitrobenzene, 50 parts of malonic acid diethyl ester and 20 parts of sodium acetate is heated to boiling until unchanged 5-aminobenzanthrone can no longer be detected. The whole is allowed to cool and the new compound formed is separated oil. According to analysis and its properties it is the ethyl ester of 11-hydr0xy-10-azaperylene-l2-carboxylic acid:

COO-C2115 (keto form) 6.7-benzo-8.l0-diazapy- It for ms'y'e'llow iieedles whichmelt at-from 319 to 320 C. It dissolves in concentrated sulphuric acid giving a rose-red coloration. The solution in alkali is yellow.

From 5-methylaminobenzanthrone and malonic acid diethyl ester-thereis obtained the corresponding N-methyl-compound which may also be obtained by the treatment of the above-mentioned 11hydroxy-10azaperylene-12-carboxylic acid ethyl ester with alkylating agents. If 5- aminobenzanthrone be reacted in the same manner with aceto-acetic acid ester, ll-hydroxyl2-acetyl-10-azaperylene is obtained, with benzoylacetic acid ester the corresponding phenyl derivative-is obtained and with cyanoacetic acid ester the corresponding cyano compound is obtained.

1l-hydroxy-lO-azaperylene itself is obtained by the treatment of 5-acetylaminobenzanthrone with alkaline agents, as"for example by heating 5-acetylaminobenzanthrone with barium oxide in the presence of nitrobenzene.

If the 5-aminobenzanth'rones be replaced by 4-aminobenzanthrones, the corresponding 6.7- benzo-lO-azapyrene derivatives are obtained.

Example 5 A mixture of 20 parts of 5-aminobenzanthrone, 40 parts of urethane and 200 parts of nitrobenzene is heated'to boiling until a sample withdrawn no longer contains unchanged 5-aminobenzan- Example 6 A mixture of parts of fi-aminobenzanthrone, 100 parts of the hydrochloride of cyanamide and 1000 parts of nitrobenzene is heated for several hours at about C. while leading in hydrogen chloride. After heating for some time to boiling and when a sample withdrawn is free from the initial material, the mixture is allowed to cool and the aminodiazaperylene formed is filtered off by suction. It has the following composition:

and dissolves in concentrated sulphuric acid giving a blue-red coloration. It forms red-yellow needles which melt at from 312 to 313 C. The solution in hydrocarbons and halogenhydrocarbons has a powerful green fluorescence.

By employing :the hydrochloride of alkylcyanamide or arylcyanamide instead of that of cyanamide itself, the corresponding alkylamino or arylamino diazaperylene are obtained. In a similar manner the hydrochloride of benzoylcyanamide and 5-aminobenzanthrone'jyields under the same conditions benzoylaminodiazaperylene.

Under similar conditions 5-phenyl-3.6-diaza.- perylene may be obtained by reacting 5-aminobenzanthrone with phenylmethylimidechloride.

By employing 4-aminobenzanthrone instead of 5-aminobenzanthrone the corresponding benzodiazapyrenesiare obtained. In a similar manner the derivatives ofrthe sai'd compounds may be obtained by starting from '4- or S-aminoben'zanthrones. containing any substituents' such as halogen atoms or alkyl-, aryl-, acyl-, acylamino-, hydroxyamino-, a1kylamino-, sulphonic-, carboxylic-, -cyanic ester-, trifluormethylor thiocyanogen groups. The said groups may also be present several times in the molecule.

' Example 7 i A mixture of 80 parts of 4-amino-5-hydroxybenzanthrone (obtainable by heating 4.5-dihydroxybenzanthrone with ammonia, parts of nitrobenzene, 320 parts of 'formamide and 50 parts of ammonium bisulphate is heated to boiling while stirring until a sample withdrawn-no longer contains initial material. After coolingv the resulting hydroxybenzodiazapyrene is filtered ofi by suction, washed and dried.

In a similar manner, by reacting formamide with dibrom-4-aminobenzanthrone, dibrombenzodiazapyrene, and from chlor-.5-aminobenzanthrone the corresponding chlordiazaperylenes are obtained.

Example 8 A mixture of 50 parts of 1.9-anthrapyrimidine, 100 parts of glycerine, 1000 parts of 66 per cent sulphuric acid and 75 parts of aniline sulphate is boiled while stirring for several hours. After cooling the reaction mixture is poured into 2000 parts of water and after adding ammonia until the solution has become alkaline, the quinoline formed is removed by means of steam and the residue is filtered oil by suction. The compound such formed in a very good yield may be purified by recrystallization and sublimation. It dissolves in concentrated sulphuric acid giving a yellow coloration and a green fluorescence and melts at from 188 to 190 C. According to anal.- ysis and all its properties it is identical to the 6.7-benzo-8.10-diazapyrene described in Example 3.

In a similar manner a chlorbenzo-diazapyrene is obtained from 5-chlor-1.9-anthrapyrimidine.

N-methyl-1.9-anthrapyridones and glycerine yield in the same manner the corresponding benzomonoazapyrene.

What I claim is:

1. An aza compound of the general formula II I I! in which a pyrimidine ring is built up from the position marked :2 to one of the positions marked 1!.

2. An aza, compound of the general formula 4. The aza compound having the formula.

wherein R stands for a member selected from ILIH,

the class consisting of hydrogen and the hy- 15 droxyl amino, alkyl and aryl groups.

3. An aza compound of the general formula 25 N A N N wherein R stands for a member selected from the class consisting of hydrogen and the hydroxyl, amino, alkyl and aryl groups.

5. The aza compound of the formula,

KARL KOEBERLE. 

